Method of making armor with transformed nanotube material

ABSTRACT

Methods for making armor and armor articles with transformed nanomaterial. This abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure and is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims, 37 C.F.R. 1.72(b).

RELATED APPLICATION

This is a division of U.S. application Ser. No. 12/657,289 filed Jan.16, 2010 now U.S. Pat. No. 8,225,704, from which the present applicationclaims priority under the Patent Laws and which is incorporated fullyherein for all purposes.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to armor made of ceramic withtransformed nanotube material and to methods for making such armor.

2. Description of Related Art

There is a wide variety of known ceramic articles and methods for makingthem. There are known ceramic articles containing carbon nanotubes andmethods for making them.

Prior patents and applications disclose a variety of carbon nanotubes,films, and coatings ceramic articles, ceramic articles containing carbonnanotubes, films, coatings and methods for making them; including, butnot limited to, those in exemplary U.S. Pat. Nos. 7,581,645; 7,578,939;7,442,414; 7,306,828; 7,122,710; 7,041,372; 6,911,260; 6,858,173;6,826,996; 6,420,293; 5,824,940; 5,618,875; 5,424,054; U.S. applicationSer. Nos. 12/189,684 filed 11 Aug. 2008; 12/025,626 filed 4 Feb. 2008;11/924,948 filed 26 Oct. 2007; 11/659,407 filed 2 Aug. 2005; 11/656,603filed 23 Jan. 2007; 11/579,750 filed 31 May 2005; 11/450,221 filed 9Jun. 2006; 11/090,259 filed 25 Mar. 2005; 10/984,619 filed 9 Nov. 2004;10/859,346 filed 3 Jun. 2004; 10/759,356 filed 16 Jan. 2004; 10/714,187filed 14 Nov. 2003; 10/536,688 filed 25 Nov. 2003; and 10/366,183 filed13 Feb. 2003; 10/182,081 filed 1 Feb. 2001; and Pct ApplicationsPCT/US2004/019015; PCT/US2006/015919 (all said patents and applicationsincorporated fully herein for all purposes).

Graphite layers, graphene ribbons, and articles with them are wellknown. Exemplary patents and applications which disclose them include,but are not limited to, U.S. Pat. Nos. 7,550,129; 7,510,762; 7,396,494;7,015,142; and 6,537,515; and U.S. application Ser. No. 12/243,165 filed10 Oct. 2008 (which is not an exhaustive list; and all said patents andapplications incorporated fully herein for all purposes).

Ceramic articles with carbon nanotubes are discussed in manypublications, including, but not limited to, in “Carbon NanotubeReinforced Ceramic Matrix Composites—A Review,” Journal of Minerals &Materials Characterization & Engineering, Volume 7, Number 4, 2008, pp.355-370. Graphene is discussed generally in many publications,including, but not limited to, in “Graphene: Carbon As Thin As Can Be,”Chemical & Engineering News, Volume 87, Number 9, Mar. 2, 2009, pp.14-20.

A wide variety of armor and armor employing ceramic material is known.Armor with ceramic and carbon nanotubes is known. Prior patents disclosevarious forms of armor, armor with ceramic material, and armor withceramic material and carbon nanotubes, including, but not limited to(and meant only as an exemplary and not an exhaustive listing); U.S.Pat. Nos. 7,513,186; 7,041,372; 6,826,996; 6,568,310; 6,112,635;5,996,115; 5,824,940; 5,763,813; 5,443,917; 5,377,935; 5,371,049;5,361,678; 5,221,807; and U.S. patent application Ser. Nos. 12/189,684filed 11 Aug. 2008; 11/656,603 filed 23 Jan. 2007; 11/450,221 filed 9Jun. 2006; and 10/859,346 filed 3 Jun. 2004.

There has long been a need, recognized by the present inventors, fordurable, effective low weight armor with carbon nanomaterial andefficient methods for making such armor.

SUMMARY OF THE PRESENT INVENTION

The present invention, in certain aspects, discloses armor whichincludes a ceramic article with a matrix of ceramic material andtransformed nanotubes, e.g. graphene ribbon-like material, produced bysubjecting nanotubes to pressure and heat, changing the nanotubes tonon-tubular material. In one aspect, the ceramic material is aluminaoxide. In one aspect, graphene ribbon-like material (“ribbons”) in thefinished article is produced by transforming (e.g. by crushing, milling,grinding, etc.) carbon nanotubes in a mixture of ceramic material. Incertain aspects the nanotubes, prior to transformation, aresingle-walled nanotubes, double walled nanotubes, surface-modifiednanotubes, multi-walled nanotubes, or combinations thereof. In oneparticular aspect, graphene ribbon-like material is added to the matrixbefore pressure is applied.

In certain aspects, the armor is a backing only (with or withoutnanotubes therein, with or without transformed nanotubes therein); orincludes a backing with at least one layer or with multiple layers ofballistic fabric interleaved with a binder material containing nanotubes(“nanotube-modified binder material”). The nanotubes may either becoated on the surface of the binder material or they may be incorporatedinto a binder material matrix. In certain aspects the nanotubes, priorto transformation, are single-walled nanotubes, double walled nanotubes,surface-modified nanotubes, multi-walled nanotubes, or combinationsthereof. The backing may be backed with protective laminate on bothsides. The backing, in one aspect, is a polymeric film with nanotubestherein and, in one particular aspect, is a nanofilm with transformednanotubes, e.g. a graphene ribbon nanofilm.

In one aspect, a laminated backing according to the present invention ismade by pressing the components at a desired pressure and temperature.In one aspect, the resulting backing is formed in a desired shape, e.g.using temperature and/or pressure. In certain aspects, the ballisticfabric has nanotubes therein and/or transformed nanotubes. Ballisticfabric includes, but is not limited to, ARAMID (trademark) fiber fabric,KEVLAR (trademark) material polyethylene ballistic fabric material, andSPECTRA (trademark) material.

In another aspect, the armor includes a backing having multiple layersof ballistic fabric which contains nanotubes (“nanotube-modifiedballistic fabric”). The nanotubes exist, in certain aspects, as acoating on the surface of the ballistic fabric; the nanotubes arefabricated (“grown”) directly on the surface of the fabric; or thenanotubes are incorporated into a matrix of the ballistic fabric. Inaddition, the nanotube-modified ballistic fabric layers may beinterleaved with a binder material. The binder material may or may notcontain nanotubes and/or transformed nanotubes, as described above. Sucha backing may then be backed with protective laminate on both sides. Thelaminated backing is made by pressing the components at a desiredpressure and temperature. In one aspect, the resulting backing is formedin a desired shape, e.g. using temperature and/or pressure. In certainaspects the nanotubes, prior to transformation, are single-wallednanotubes, double walled nanotubes, surface-modified nanotubes,multi-walled nanotubes, or combinations thereof.

In one aspect, the armor according to the present invention includes abacking with multiple layers of ballistic fabric interleaved with thinfilms of nanotubes, commonly referred to as “buckypaper”. In certainaspects the buckypaper nanotubes are single-walled nanotubes, doublewalled, nanotubes, multi-walled nanotubes, surface-modified nanotubes,or combinations thereof. In addition, the backing may containnanotube-modified ballistic fabrics and/or nanotube-modified bindermaterials as described above. Such a backing according to the presentinvention may then be backed with protective laminate on both sides.This laminated backing is made by pressing the components at a desiredpressure and temperature. In one aspect, the resulting backing is formedin a desired shape, e.g. using temperature and/or pressure.

In another aspect, a backing according to the present invention iscombined with other material(s) and/or structure(s) to produce amulti-component armor usable on things and on persons.

In one aspect, the ceramic article is a matrix of ceramic material andtransformed nanotubes e.g. graphene ribbon-like material (“ribbons), inwhich the ceramic material is sintered together, with the transformedmaterial incorporated into the sintered matrix.

In certain aspects, a ceramic article according to the present inventionis made using a mold with a particular shape. The mold may be anydesired shape to produce a ceramic article of a desired shape (e.g., butnot limited to, the shapes shown in the drawing figures herein). Inother aspects, an article made according to the present invention isetched, cut, sanded, machined, water-jet cut, or laser cut to achieve adesired shape.

In certain aspects, a finished ceramic article according to the presentinvention with ceramic material and transformed nanotubes, e.g. grapheneribbons, also contains one or more of: single-walled nanotubes;double-walled nanotubes; multi-walled nanotubes; surface-modifiednanotubes, and/or graphene ribbons not produced by crushing, etc. duringmaking of a ceramic article.

Heat may be applied to a matrix according to the present invention usingany suitable known heating apparatus and any suitable known method,including, but not limited to, conventional oven sintering, microwaveassisted sintering, and spark plasma sintering.

Filed on even date herewith, co-owned with the present invention, andincorporated fully herein for all purposes is U.S. patent applicationSer. No. 12/657,244 entitled “Ceramic Articles and Methods.” Filed oneven date herewith, co-owned with the present invention, andincorporated fully herein for all purposes is U.S. patent applicationSer. No. 12/657,288 entitled “Metallized Nanotubes.”

Accordingly, the present invention includes features and advantageswhich are believed to enable it to advance armor technology.Characteristics and advantages of the present invention described aboveand additional features and benefits will be readily apparent to thoseskilled in the art upon consideration of the following description ofpreferred embodiments and referring to the accompanying drawings.

Certain embodiments of this invention are not limited to any particularindividual feature disclosed here, but include combinations of themdistinguished from the prior art in their structures, functions, and/orresults achieved. Features of the invention have been broadly describedso that the detailed descriptions of embodiments preferred at the timeof filing for this patent that follow may be better understood, and inorder that the contributions of this invention to the arts may be betterappreciated. There are, of course, additional aspects of the inventiondescribed below and which may be included in the subject matter of theclaims to this invention. Those skilled in the art who have the benefitof this invention, its teachings, and suggestions will appreciate thatthe conceptions of this disclosure may be used as a creative basis fordesigning other structures, methods and systems for carrying out andpracticing the present invention. The claims of this invention are to beread to include any legally equivalent devices or methods which do notdepart from the spirit and scope of the present invention.

What follows are some of, but not all, the objects of this invention. Inaddition to the specific objects stated below for at least certainembodiments of the invention, other objects and purposes will be readilyapparent to one of skill in this art who has the benefit of thisinvention's teachings and disclosures. It is, therefore, an object of atleast certain embodiments of the present invention to provide theembodiments and aspects listed above and:

New, useful, unique, efficient and nonobvious multi-layered armor whichincludes ceramic and transformed nanotubes, e.g. but not limited tographene ribbon-like material, produced by subjecting nanotubes topressure and heat;

New, useful, unique, efficient and nonobvious laminated multi-layeredarmor material which includes ceramic transformed nanotubes, e.g., andgraphene ribbon-like material;

New, useful, unique, efficient and nonobvious multi-layered armor whichincludes ceramic and ribbons according to the present invention, and,optionally, additional components; and

New, useful, unique, efficient and nonobvious ceramic articles withribbons.

The present invention recognizes and addresses the problems and needs inthis area and provides a solution to those problems and a satisfactorymeeting of those needs in its various possible embodiments andequivalents thereof. To one of skill in this art who has the benefits ofthis invention's realizations, teachings, disclosures, and suggestions,various purposes and advantages will be appreciated from the followingdescription of certain preferred embodiments, given for the purpose ofdisclosure, when taken in conjunction with the accompanying drawings.The detail in these descriptions is not intended to thwart this patent'sobject to claim this invention no matter how others may later attempt todisguise it by variations in form, changes, or additions of furtherimprovements.

The Abstract that is part hereof is to enable the U.S. Patent andTrademark Office and the public generally, and scientists, engineers,researchers, and practitioners in the art who are not familiar withpatent terms or legal terms of phraseology to determine quickly, from acursory inspection or review. the nature and general area of thedisclosure of this invention. The Abstract is neither intended to definethe invention, which is done by the claims, nor is it intended to belimiting of the scope of the invention or of the claims in any way.

It will be understood that the various embodiments of the presentinvention may include one, some, or all of the disclosed, described,and/or enumerated improvements and/or technical advantages and/orelements in claims to this invention.

Certain aspects, certain embodiments, and certain preferable features ofthe invention are set out herein. Any combination of aspects or featuresshown in any aspect or embodiment can be used except where such aspectsor features are mutually exclusive.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

A more particular description of embodiments of the invention brieflysummarized above may be had by references to the embodiments which areshown in the drawings which form a part of this specification. Thesedrawings illustrate embodiments preferred at the time of filing for thispatent and are not to be used to improperly limit the scope of theinvention which may have other equally effective or legally equivalentembodiments.

FIG. 1 is a schematic view of a method according to the presentinvention.

FIG. 2A is a perspective view of a tile according to the presentinvention.

FIG. 2B is a perspective view of a disc according to the presentinvention.

FIG. 2C is a perspective view of a panel according to the presentinvention.

FIG. 2D is a perspective view of a cylinder according to the presentinvention.

FIG. 2E is a perspective view of a pyramid according to the presentinvention.

FIG. 2F is a perspective view of a sphere according to the presentinvention.

FIG. 2G is a perspective view of a cone according to the presentinvention.

FIG. 2H is a side view of a knife according to the present invention.

FIG. 2I is a side view of a key according to the present invention.

FIG. 2J is a side view of a gear according to the present invention.

FIG. 2K is a side view of a hook according to the present invention.

FIG. 2L is a side view of a nut-bolt combination according to thepresent invention.

FIG. 2M is a side view of a chain according to the present invention.

FIG. 2N is a top view of a chain according to the present invention.

FIG. 2O is a side view of a screw according to the present invention.

FIG. 2P is a side view of a scalpel according to the present invention.

FIG. 2Q is a cross-section view of a bearing structure according to thepresent invention.

FIG. 2R is a side view of a drill bit according to the presentinvention.

FIG. 2S is a side view of a mill according to the present invention.

FIG. 2T is a side view of a reamer according to the present invention.

FIG. 2U is a perspective view of a pipe according to the presentinvention.

FIG. 2V is a side view of a universal joint according to the presentinvention.

FIG. 2W is a side view partially in cross-section of a drill bitaccording to the present invention.

FIG. 2X is a perspective view of a drill bit according to the presentinvention.

FIG. 2Y is a side view of pliers according to the present invention.

FIG. 3A is a cross-section view of a backing made according to thepresent invention.

FIG. 3B is a cross-section view of a backing as in FIG. 3A formedaccording to the present invention.

FIG. 3C is a side view of a backing according to the present invention.

FIG. 4A is a cross-section view of armor according to the presentinvention.

FIG. 4B is a top view of the armor of FIG. 4A.

FIG. 4C is a cross-section view of armor according to the presentinvention.

FIG. 5A is a cross-section view of armor according to the presentinvention.

FIG. 5B is a cross-section view of armor like that of FIG. 5A.

FIG. 5C is a cross-section view of armor according to the presentinvention.

FIG. 5D is a top view of armor according to the present invention.

FIG. 5E is a top view of armor according to the present invention.

FIG. 5F is a top view of armor according to the present invention.

FIG. 6A is a perspective partially cut-away view of armor according tothe present invention.

FIG. 6B is a perspective partially cut-away view of armor according tothe present invention.

FIG. 7A is a cross-section view of armor according to the presentinvention.

FIG. 7B is a cross-section view of armor according to the presentinvention.

FIG. 7C is a cross-section view of armor according to the presentinvention.

FIG. 7D is a cross-section view of armor according to the presentinvention.

FIG. 8 is a perspective exploded view of armor according to the presentinvention.

FIG. 9 is a cross-section view of armor according to the presentinvention.

FIG. 10 is a perspective partially cross-sectional view of armoraccording to the present invention.

FIG. 11 is a cross-section view of armor according to the presentinvention.

FIG. 12A is a front view of an armor vest according to the presentinvention.

FIG. 12B is a front view of a tile according to the present invention.

FIG. 12C is a cross-section view of material according to the presentinvention used to make a tile as in FIG. 12B.

Certain embodiments of the invention are shown in the above-identifiedfigures and described in detail below. Various aspects and features ofembodiments of the invention are described below and some are set out inthe dependent claims. Any combination of aspects and/or featuresdescribed below or shown in the dependent claims can be used exceptwhere such aspects and/or features are mutually exclusive. It should beunderstood that the appended drawings and description herein are ofcertain embodiments and are not intended to limit the invention or theappended claims. On the contrary, the intention is to cover allmodifications, equivalents and alternatives falling within the spiritand scope of the invention as defined by the appended claims. In showingand describing these embodiments, like or identical reference numeralsare used to identify common or similar elements. The figures are notnecessarily to scale and certain features and certain views of thefigures may be shown exaggerated in scale or in schematic in theinterest of clarity and conciseness.

As used herein and throughout all the various portions (and headings) ofthis patent, the terms “invention”, “present invention” and variationsthereof mean one or more embodiments, and are not intended to mean theclaimed invention of any particular appended claim(s) or all of theappended claims. Accordingly, the subject or topic of each suchreference is not automatically or necessarily part of, or required by,any particular claim(s) merely because of such reference. So long asthey are not mutually exclusive or contradictory any aspect or featureor combination of aspects or features of any embodiment disclosed hereinmay be used in any other embodiment disclosed herein. The drawingfigures present the embodiments preferred at the time of filing for thispatent.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 illustrates schematically a method 10 according to the presentinvention. Ceramic material 12 is processed in a processing apparatus 14and then processed ceramic material is introduced into a mold 20. In oneaspect the processing apparatus 14 produces ceramic material within adesired size (largest dimension) range. In one particular aspect theceramic material is aluminum oxide (alumina) particles and theprocessing apparatus 14 is a dry ball mill which mills the particles toa median size (largest dimension) of about 700 nanometers (in one aspectwithin a range of between 10 nanometers and 100 microns), with themilled particles having a surface area between 3.5 to 4.5 square metersper gram.

Carbon nanotube material 16 is processed by a processing method 18 andthen processed (“transformed”) nanotube material is introduced into themold 20. In one aspect, the carbon nanotube material is multi-wallednanotubes. In other aspects, it is any desired nanotube material,including, but not limited to, any nanotube material disclosed orreferred to herein, and, e.g. functionalized nanotubes. In one aspect ofa method 18, the nanotubes are suspended in ethanol in a bath using anyknown suitable sonication method for an amount of time sufficient toachieve deagglomeration of bundles of nanotubes, to create a metastablenanotube suspension, and to wet the nanotube surfaces with ethanol, e.g.for about thirty minutes. In one particular aspect, a two-vesselsonication method is used with transducers and wave transfer liquid. Theresulting nanotube-ethanol mixture is added to an aluminum oxide-ethanolmixture and the resulting mixture is sonicated. The resulting sonicatedmixture is then stirred to produce a homogeneous) mixture, e.g. forabout one hour. The stirred mixture is poured into a container so thatthe ethanol in the mixture evaporates, e.g. the container is a bakingdish and the mixture is allowed to sit overnight, e.g. about eight toten hours, for ethanol evaporation. The resulting dried material is thenbaked (to insure all water and ethanol are removed), e.g. at eightydegrees centigrade in a vacuum oven for two to three hours. Theresulting material is then milled in a ball mill, e.g. to within a sizerange between ten nanometers and one hundred microns. Then milledmaterial is introduced into the mold 20 producing aceramic-material/nanotube mixture 22 in the mold 20.

In one aspect the alumina and multi-walled nanotube material in the moldis between 0.1% to 10% by weight nanotubes, the remainder alumina. Inone particular aspect, the material in the mold is between 0.1% to 1.0%by weight nanotubes.

A compression member 30 is applied to the mixture 22 in the mold at apressure sufficient to achieve crushing of the nanotubes producinggraphene ribbon-like material (“ribbons”) in the mixture. In one aspect,the mixture 22 is compressed at between 10,000 psi and 100,000 psi. Acompressed mixture 24 is produced. The produced ribbon-like material isone to ten microns in length and one to one hundred nanometers wide (inone aspect, one to ten nanometers wide).

The compressed mixture 24 is sintered in a furnace 40 producing afinished ceramic article 50. In one particular aspect in which theceramic material is the alumina described above and the nanotubes arethe multi-walled carbon nanotubes described above, the mixture 24 issintered at about 1600 degrees C. for 0.5 hours to 24 hours hours in aninert (e.g. nitrogen, argon) atmosphere. The heated material is thencooled (using any suitable known cooling technique and/or coolingapparatus).

Prior to solvent evaporation and pressing, and/or prior to sintering,additional nanotube material and/or graphene ribbon-like material may beintroduced into the mixture 24.

The mold 20 may be of any desirable shape and configuration to produce afinished article of any desirable shape and configuration.

In addition to producing finished articles useful in armor, methodsaccording to the present invention are useful for producing items,things, parts, tools and objects made, in whole or in part, withtransformed nanotubes, e.g., graphene ribbon-like material as describedabove. FIGS. 2A-2Y present a variety of exemplary items, etc. made withceramic material with transformed nanotubes, e.g. graphene ribbons,according to the present invention. These depictions are not meant to beexhaustive of all the items, etc. that can be made with the materialaccording to the present invention, but are only presented here as someof the examples of such items, etc. For each of the things in FIGS.2A-2Y, as described below transformed nanotubes of any type maybe usedinstead of (or in addition to) the stated graphene ribbon-like material,according to the present invention.

FIG. 2A shows a tile 102 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2B shows a disc 104 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2C shows a panel 106 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2D shows a cylinder 108 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2E shows a pyramid 110 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2F shows a sphere 112 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2G shows a cone 111 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2H shows a knife 114 made with ceramic material with ribbonsaccording to the present invention. A knife blade 113 and/or a handle115 may be made from the material according to the present invention.

FIG. 2I shows a key 116 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2J shows a gear 118 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2K shows a hook 120 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2L shows a nut-bolt combination 122 made with ceramic material withribbons according to the present invention with a bolt 119 and/or a nut121 made with material according to the present invention.

FIG. 2M shows a chain 122 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2N shows a chain 124 made with ceramic material with ribbonsaccording to the present invention.

Any known connector may be made of material according to the presentinvention (with ceramic and transformed nanotubes, e.g., but not limitedto, graphene ribbon-like material) e.g., but not limited to, brads,tacks, rivets, bolts, nails and screws. FIG. 20 shows a screw 126 madewith ceramic material with ribbons according to the present invention.

Surgical, dental, and orthodontic tools may be made, in whole or inpart, with material according to the present invention.

FIG. 2P shows a scalpel 128 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2Q shows a bearing structure 130 made with ceramic material withribbons according to the present invention with bearings 129 and/orbearing support 131 made with material according to the presentinvention.

It is within the scope of the present invention for all or part of abit, mill or reamer to be made of (or coated with) material according tothe present invention, including, but not limited to bit bodies, millbodies, reamer bodies, cutting blades, milling blades, reaming blades,cutting surfaces, cutters, cutting inserts, milling surfaces, and/orreaming surfaces for bits, mills, and/or reamers for metal working, woodworking, machining and/or for wellbore downhole drilling, milling andreaming. It is within the scope of the present invention for all or partof a valve (e.g., valve body, valve seat, valve member, ball) to be madeof material according to the present invention.

FIG. 2R shows a drill bit 132 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2S shows a mill 134 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2T shows a reamer 136 made with ceramic material with ribbonsaccording to the present invention.

FIG. 2U shows a pipe 138 made with ceramic material with ribbonsaccording to the present invention. Optionally a threaded area 137and/or a threaded area 139 is made with (or coated with) materialaccording to the present invention.

FIG. 2V shows a universal joint 140 made with ceramic material withribbons according to the present invention.

FIG. 2W shows a drill bit 142 made with ceramic material with ribbonsaccording to the present invention with roller cones 141, bearings 143,145 with body 147 and/or seal 149 made with material according to thepresent invention.

FIG. 2X shows a drill bit 150 made with ceramic material with ribbonsaccording to the present invention with a body 151, blades 153, and/orcutters (or cutting inserts) 155 made with material according to thepresent invention.

Hand tools, including, but not limited to wrenches, screwdrivers, awls,chisels, hammers, saws, pliers, scissors, may be made, in whole or inpart, with material according to the present invention.

FIG. 2Y shows pliers 160 made with ceramic material with ribbonsaccording to the present invention.

U.S. Pat. No. 6,420,293 discloses ceramic matrix nanocompositescontaining carbon nanotubes and methods for making them. Unlike thepresent invention, U.S. Pat. No. 6,420,293 has no teaching or suggestionof using graphene or graphene ribbon-like material in a ceramic articleand no teaching or suggestion of methods for producing transformednanotubes, e.g. ribbons, in a ceramic mixture. The present inventionprovides various new and nonobvious improvements for the articles andthe methods of U.S. Pat. No. 6,420,293 (which patent is incorporatedfully herein for all purposes).

The present invention discloses, in certain aspects, a ceramic matrixcomposite which includes graphene ribbon-like material, andnanocrystalline ceramic material (and/or ceramic powder), with orwithout other nanotube material and methods for producing ceramicarticles with such material. The graphene ribbon-like material (fortransformed nanotubes) may be made during the process of making theceramic matrix composite from nanotube material; or ribbons may be mixedwith ceramic material. The nanocrystalline ceramic material (or ceramicpowder) may be a ceramic metal oxide. The metal of the ceramic metaloxide may be aluminum, titanium, zirconium, magnesium, yttrium, orcerium. In particular, the metal may be aluminum, titanium or zirconium.Specifically, the metal oxide may be alumina. In certain aspects, theamount of ribbons in the composite is about 0.5 to 50 parts by volume;the amount of ceramic matrix is about 50 to 99.5 parts by volume and, inone particular aspect, the amount of ribbons may be 1 to 20 parts byvolume, and the amount of ceramic matrix about 80 to 99 parts by volume.The ceramic material may be a carbide or nitride, e.g., silicon carbide,boron nitride, or boron carbide.

In certain aspects, the present invention provides methods for producingceramic articles including combining transformed nanotubes, e.g.,ribbons, according to the present invention and a ceramic matrix havingat least one nanocrystalline ceramic material; forming an articletherefrom; and heating, optionally sintering, the article under elevatedpressure at elevated temperature. Optionally, the ribbons are made bycrushing nanotube material which has been mixed with the ceramicmaterial. The nanocrystalline ceramic material may be a ceramic metaloxide. The metal of the ceramic metal oxide may be aluminum, titanium,zirconium, magnesium, yttrium, or cerium. In particular, the metal maybe aluminum, titanium or zirconium. In one aspect, the metal oxide isalumina. In certain aspects, the amount of ribbons in the composite isabout 0.5 to 50 parts by volume; the amount of ceramic matrix is about50 to 99.5 parts by volume. In particular aspects, the amount of ribbonsis 1 to 20 parts by volume, and the amount of ceramic matrix about 80 to99 parts by volume.

FIG. 3A shows an exploded view of a backing 200 (armor) according to thepresent invention (the drawing is not to scale) which includes multiplelayers of ballistic fabric 202, which may be any known ballistic fabric,including, but not limited to KEVLAR (Trademark) material, ARAMID(Trademark) fabric material, SPECTRA SHIELD (Trademark) material, andpolyethylene ballistic material. Between fabric layers 202 is a layer(or layers) 204 of binder material to (any disclosed herein). In oneparticular aspect, the binder material is sprayed onto the fabric. Inone aspect the binder material is any suitable known binder materialwith or without nanotubes therein. The binder material can be a sheet ofplastic, or an epoxy coating, or a spray-on adhesive.

In one aspect the binder 204 is an armor article made according to thepresent invention which contains carbon nanotubes. In one aspect thebinder 204 is a thin film of carbon nanotubes (“buckypaper”). In oneaspect, the binder 204 contains carbon nanotubes and/or grapheneribbon-like material. Any binder or film according to the presentinvention can also include a suitable adhesive (with or withoutnanotubes therein, with or without ribbons therein) to facilitateadherence to fabric, e.g., but not limited to, spray adhesive 911 from3M or ABF spray adhesive. In certain aspects, the layers 204 arethermoplastic nanocomposite film which has carbon nanotubes (as thematerial in U.S. patent application Ser. No. 12/025,662 filed 4 Feb.2008).

In certain particular aspects the film 204 is a thermoplasticpolyurethane (or any suitable thermoplastic or hot melt adhesive) withor without added nanotubes or added ribbons. In one aspect, the binder204 is a thermoplastic sheet with ten milligrams of carbon nanotubes perthree grams of thermoplastic material.

In certain aspects, nanotubes or ribbon-like material is present in thebinder at 0.001% to 10% by weight. In certain aspects, the fabric 202has between 0.1% to 10% by weight nanotubes or ribbon-like material(either on a fabric surface or surfaces or in the fabric).

To form a backing according to the present invention a laminate layer206 is placed on each side of the outermost films 204 and in a pressapparatus, the combination is pressed, e.g. at between 100 and 10,000psi while heated, e.g. to between 25 degrees C. and 300 degrees C. Theresulting backing 200 can be formed into a desired shape by applyingpressure to it, e.g., with a mold of desired shape and/or by heating it,e.g. in a heated press and then bending it or otherwise mechanicallyshaping it. FIG. 3B illustrates a backing 200 a which has been formedwith a ninety-degree bend. A backing according to the present inventionmay be any suitable thickness and, in certain aspects, ranges between0.1 and 10 inches thick. A backing according to the present inventionmay be formed into any desired shape. Such a backing may itself be usedas “soft” armor, e.g. for vehicles, aircraft (planes, helicopters, etc),and boats, or for parts thereof.

It is within the scope of this invention to use any desired number offabric layers 202 including, but not limited to one, two, three, four,five, six, seven, eight, nine or ten. In certain aspects the fabriclayers 202 are 0.0001 inches and 0.01 inches thick. In certain aspects,the binders or films 204 are between 0.0001 and 0.01 inches thick.

FIG. 3C shows a backing 200 b, like the backings 200 or 200 a, which isused as armor for a thing or for a person.

FIGS. 4A and 4B show an armor structure 210 according to the presentinvention which has a backing 200 c (like any backing described aboveaccording to the present invention) to which are adhered tiles 212 usingadhesive 214. The tiles 212 may be any known tile used in armor or thetiles 212 may be made as described above by a method according to thepresent invention as an article according to the present invention withceramic and graphene ribbons.

In one aspect, the adhesive 214 (and any adhesive in any backing, armoror armor structure according to the present invention) is any suitableknown adhesive. In one particular aspect the adhesive 214 is a polymerepoxy adhesive, (e.g. as in U.S. application Ser. No. 10/559,905 filed16 Jun. 2004). Any adhesive disclosed or referred to herein may,according to the present invention, have carbon nanotubes and/ortransformed nanotubes therein, or both, as taught by the presentinvention.

An adhesive 216 is used between adjacent tiles 212. In one aspect, theadhesive 216 is any suitable known adhesive. In one aspect, the adhesive216 is chosen for its elongation ability and its ability to withstandimpacts.

The tiles 212 may have any suitable dimensions and any suitable shape(e.g. but not limited to, rectangular, square, triangular,parallelogram, pentagonal and hexagonal). In one particular aspect, thetiles are square and are two inches by two inches.

In adhering the tiles 212 to the backing 200 c, the tiles 212 may bepressed against the backing 200 c with heat, using a heated press with aheated platen(s) or roller(s).

As shown in FIG. 4B, the tiles 212 are arranged in order with tiles 212in one row, as viewed in FIG. 4B, lined up with tiles 212 in anotherrow. Also, it is within the scope of the present invention to stacktiles one, two, three, etc. deep and, in one aspect, to have the stackedtiles line up with each other; or (as shown in FIG. 5C) to have stackedtiles offset from each other.

It is also within the scope of the present invention to stack tiles ofdifferent thickness; e.g., as shown in FIG. 4C, a backing 200 d made asany backing according to the present invention described above, hastiles 212 in two columns with tiles 218 of a different thickness in anintermediate column. Different tiles may also, according to the presentinvention, be used in different rows (e.g. as in the rows of FIG. 4B).

FIG. 5A shows a backing 200 e made as any backing above according to thepresent invention which has tiles 222 adhered thereto. As shown in FIG.5B, tiles 222 in adjacent rows are offset with respect to each other.Adhesives 214 and 216 are used as in the structure of FIG. 4A.

Tiles according to the present invention may be used in patternsdifferent from those in preceding figures. For example, see FIGS. 5D-5F.FIG. 5D shows armor 224 according to the present invention which is likethe armor structure 210, but in which tiles 224 t are in a diamondpattern employing partial tiles 224 p. Adhesive used with these tiles islike that of the structures of FIGS. 4A-5C.

FIG. 5E shows armor 226 according to the present invention which is likethe armor structures of FIGS. 4A-5D, but which has tiles 226 t, asviewed from above, of a generally hexagonal shape. Partial tiles 226 pare used at the structure's edges. Adhesive used with these tiles islike that of the structures of FIGS. 4A-5C.

FIG. 5F shows armor 228 according to the present invention which is likethe armor structures of FIGS. 4A-5D, but which has tile 228 t which aregenerally triangular as viewed from above and partial tiles 228 p atedges. Adhesive used with these tiles is like that of the structures ofFIGS. 4A-5C.

As shown in FIG. 5C, two (three, four, five or more) columns of tiles222 may be used as in a backing 200 f (made as any backing describedabove according to the present invention) with tiles in one columnoffset from those in an adjacent column.

The present invention provides improvements to the laminate barrierpanel of U.S. Pat. No. 6,568,310 (incorporated fully herein for allpurposes) and the panel according to the present invention is new andnonobvious compared to the panel of this patent. This patent has noteaching or suggestion to use carbon nanotubes, graphene or grapheneribbons as taught by the present invention.

A panel 230 according to the present invention as shown in FIG. 6A has alayer 234 between two layers 236 of a mesh or mail material. A layer 238of body material is located outwardly of the layers 236. Optionally, thelayers 238 are covered by sheets or laminate 240. Optionally, adhesiveis used between adjacent layers and/or to secure the sheets 20 to thelayers 238. The layers 236 may be mesh or mail layers.

It is within the scope of the present invention to spray a film 239(shown on a side of the layer 234) containing carbon nanotubes and/orribbons according to the present invention onto any, some, or allsurfaces of all layers of the panel 230 (as is true also for anyembodiment herein with layers or plates). It is within the scope of thepresent invention to include ribbons according to the present inventionin any, some, or all layers of the panel 230. It is within the scope ofthe present invention for any, some or all of the layers 234, 236,and/or 238 to be a suitable article with ceramic and ribbons accordingto the present invention made by any method according to the presentinvention described above.

FIG. 6B shows a panel 250 according to the present invention which has acentral layer 252 with a mesh or mail layer 254 on either side. Layers256 of relatively light weight body material are on sides of the layers254 and layers 258 are on sides of the layers 256. Layers 253 are onsides of the layers 256. The layers 252, 253, 256 and/or the layers 258(as may be the layer 234, FIG. 6A) are, in one aspect made of ballisticmaterial which includes ceramic and ribbons according to the presentinvention. As with the panel 230, the layers of the panel 250 areconnected together with an adhesive.

It is within the scope of the present invention to spray a film 259(shown on a side of the layer 252) containing carbon nanotubes and/orgraphene ribbons onto any, some, or all surfaces of all layers of thepanel 250. It is within the scope of the present invention to includeribbons according to the present invention in any, some, or all layersof the panel 250. It is within the scope of the present invention forany, some or all of the layers 252, 254, and 256 to be a suitablearticle with ceramic and ribbons made by any method according to thepresent invention described above.

The present invention provides new and nonobvious armor as compared tothe composite armor of U.S. patent application Ser. No. 11/656,603 filedJan. 23, 2007 (incorporated fully herein for all purposes). This patentapplication has no teaching or suggestion of using carbon nanotubes,graphene or graphene ribbon-like material as taught by the presentinvention.

An armor structure 260 according to the present invention as shown inFIG. 7A has a layer 262 (e.g. 5 mm to 60 mm thick) provided to disruptan incoming projectile. Any, some, or all of the components of thislayer 262 described below may be a suitable article made according tothe present invention as described above or may have ceramic andgraphene ribbons as described above.

In one aspect the layer 262 includes tiles 264 (made in certain aspectsas any tile described above according to the present invention) retainedwith a retaining material 266 (e.g. any suitable adhesive or polymer).Each tile 264 may be polygonal with a base 268 (e.g. bases between 30 mmand 60 mm wide). A backing 274 is adjacent the layer 262 (optionally,with a layer of adhesive 272 between them). The backing 274 may be likeany backing according to the present invention described above or may bethe lacking of the above-identified patent application Ser. No.11/656,603. The backing 274 may include a reinforcing layer 276 encasedwith a polymer 278. An optional spall layer 279 may be provided in thematerial 266. The spall layer may be any suitable fragment-containingmaterial, e.g. synthetic plastic, thermoplastic, polycarbonate, orpolymeric.

FIG. 7B shows an armor structure 280 according to the present inventionwhich has a tile layer 282, confining layers 284, a ceramic layer 286and a backing layer 288. The tile layer 282 may be made as any tileaccording to the present invention described above. The confining layers284 may be any backing according to the present invention describedabove, a layer of ribbons (and/or of carbon nanotubes) according to thepresent invention, or a metal or fiber reinforced composite (with orwithout ribbons, with or without carbon nanotubes). The ceramic layer286 may be any suitable backing according to the present inventiondescribed above or it may be a suitable article according to the presentinvention with ceramic, carbon nanotubes, and/or ribbons according tothe present invention as described above. Layers of the armor structure280 may be adhered together with adhesive and any, some, or all of thelayers may have a film with graphene ribbons and/or carbon nanotubesthereon.

FIG. 7C shows an armor structure 290 according to the present inventionwhich has a tile layer 294 between adhesive layers 292. A strengtheninglayer 296 is provided between the layers 292. A backing layer 298 isprovided adjacent one of the layers 292. The tile layer 294 may be anytile or tiles according to the present invention described above; asuitable backing according to the present invention (any as describedabove); a layer including ceramic and graphene ribbons; or a suitablearticle according to the present invention (any as described above) withceramic and graphene ribbons. The adhesive layers 292 may be anysuitable known adhesive or, according to the present invention, anadhesive with nanotubes and/or ribbons. The layer 296 may be anysuitable backing according to the present invention or any suitablearticle according to the present invention described above or a glasslayer of strengthened glass; glass and ceramic; or glass, ceramic andgraphene ribbons and/or with carbon nanotubes. The layer 298 may be anybacking according to the present invention or article according to thepresent invention described above.

FIG. 7D shows an armor structure 300 according to the present inventionwhich has ceramic layers 306 encased in an optional shell (e.g. cam orcylinder) 308 with optional confining layers 304 and a backing layer302. The confining layers 304 may be like the layers 54 in U.S.application Ser. No. 11/656,603 or they may be any backing according tothe present invention or article according to the present inventiondescribed above. Optionally the confining layer may contain ribbonsand/or nanotubes (e.g but not limited to carbon nanotubes) according tothe present invention or ceramic with ribbons.

As with the layers of the structures of FIGS. 7A-7C the layers of thestructure 300 may be adhered together with suitable adhesive. As withany layer, article, backing or component of any of the disclosures ofFIGS. 4A-12D, any layer of the structure 300 may have a film thereonwhich includes graphene ribbons and/or carbon nanotubes and/or is likeany film according to the present invention described above.

The present invention provides new and nonobvious modular panels whichare neither taught by nor suggested by U.S. application Ser. No.12/189,684 filed Aug. 11, 2008 (incorporated fully herein for allpurposes). This patent has no teaching or suggestion to use carbonnanotubes, graphene or ribbons according to the present invention astaught by the present invention. FIG. 8 shows a panel 320 according tothe present invention with layers 321, 322, 323, 324, 325, 326, 327, 328and 329, with adjacent layers connected to each other, e.g. withadhesive between layers. In one aspect, layers 322-324 and 327, 328 arewoven layers, any one, two or all of which may be deleted according tothe present invention; any one, two, three or all of which may be madeof material that includes ceramic and ribbons according to the presentinvention; and any one, two, three or all of which may be any suitablebacking according to the present invention or any suitable articleaccording to the present invention as described above. In one aspectthese layers 322-324, 327 and 328 are woven polypropylene with athickness between 0.005 and 0.006 inches (e.g. 0.132 mm) and a weight ofabout 0.02 lbs. per square foot. In one aspect the polypropylene iscoated (e.g. sprayed) with carbon nanotubes and/or with grapheneribbon-like material. In another aspect the woven material is a mixtureof polypropylene and graphene ribbon-like material and/or carbonnanotubes. In one aspect the layers (or any of them) 322-324 and/or 327,328 are any suitable backing according to the present invention or anysuitable article according to the present invention as described above.

Layers 321, 325, and 329 are planar layers made, e.g., of: polyurethanefilm 0.010 to 0.015 inches thick; a film of polyurethane and grapheneribbon-like material; a film of polyurethane, ribbons and carbonnanotubes; or a film of polyurethane and carbon nanotubes. In one aspectthe film is any suitable film according to the present inventiondescribed above. Any one, two or all the layers 321, 325, 329 may bedeleted.

Layer 326, made of any suitable material of sufficient strength(including, but not limited to, materials as disclosed in U.S.application Ser. No. 12/189,684 or any of these materials with grapheneribbons) encapsulates rods 330. Optionally the rods are deleted. In oneaspect the layer 326 is about an inch thick. In one aspect the rods 330are about an inch in diameter. The rods may be made of any suitablematerial including, but not limited to, those disclosed in U.S.application Ser. No. 12/189,684 or these materials with grapheneribbon-like material and/or with carbon nanotubes as taught by thepresent invention.

In one aspect the layer 326 is any suitable backing according to thepresent invention or suitable article according to the present inventiondescribed above. In one aspect, the rods 330 are an article (of rodshape) as any such article according to the present invention asdescribed above. Optionally the layer 326 is deleted.

The present invention provides new and nonobvious armor which is neithertaught nor suggested by U.S. application Ser. No. 10/094,849 filed Mar.4, 2002 (incorporated fully herein for all purposes). This patent has noteaching or suggestion to use carbon nanotubes, graphene or ribbons astaught by the present invention. FIG. 9 shows armor 340 according to thepresent invention with a core 342 having spaces 344 each containing one(or at least one) insert 350. Sheets 344, 346 (either or both of whichmay be deleted) are on sides of the core 342.

In certain aspects, each insert 350 is made of ceramic;

ceramic with carbon nanotubes; ceramic with ribbons according to thepresent invention; or ceramic with ribbons according to the presentinvention and carbon nanotubes. In one aspect each insert 350 is a tileaccording to the present invention as any tile according to the presentinvention described above (or as in FIG. 12B), or an article accordingto the present invention as any such article described above.

In one aspect the core 342 is made of any material disclosed in U.S.application Ser. No. 10/094,849; any such material with carbonnanotubes; any such material with graphene ribbon-like material; or anysuch material with carbon nanotubes and ribbons according to the presentinvention. In one aspect the core 342 is a suitable article according tothe present invention as any such article described above with thespaces 344. The spaces 344 may be any chosen shape to accommodateinserts 350 of any chosen shape, including, but not limited to, anyshape as disclosed in FIGS. 2A-2Y, 4A, 7A and 8.

Sheets 344, 346 may be any sheet disclosed in U.S. application Ser. No.10/094,849; any such sheet with carbon nanotubes; any such sheet withribbons according to the present invention; or any such sheet withcarbon nanotubes and ribbons according to the present invention. Incertain aspects the sheets 344, 346 are any suitable backing accordingto the present invention or any suitable article according to thepresent invention disclosed above.

The present invention discloses new and nonobvious armor which isneither taught nor suggested by U.S. Pat. No. 5,221,807 (incorporatedfully herein for all purposes). This patent has no teaching orsuggestion to use carbon nanotubes, graphene or graphene ribbon-likematerial as taught by the present invention. FIG. 10 shows armor 360according to the present invention has a plate 362, a plate 364, a layer366 between the plates, and, optionally, a plate 368. Each of theseplates and layers may be of material as described in U.S. Pat. No.5,221,807; of such material with carbon nanotubes; of such material withribbons according to the present invention; or of such material withcarbon nanotubes and ribbons according to the present invention.

In certain aspects, the plates 362, the plate 364, and/or the plate 368are any suitable backing according to the present invention or anysuitable article according to the present invention described above.They may be solid or, as shown in FIG. 10, they may have a series ofopenings or spaces (as may any article according to the presentinvention described above). As is true for any embodiment of the presentinvention in which an item, layer, plate, backing or article has anopening, openings, a space, or spaces, each space 361 in the plate 366may be filled with material 363 including ceramic and grapheneribbon-like material (one such space indicated with material 363 in FIG.10) and each opening 365 in the plate 364 may be filled with material367 including ceramic and graphene ribbon-like material (one such spaceindicated with material 367 in FIG. 10). The material 363 and/or thematerial 367 may be any suitable backing according to the presentinvention or any suitable article according to the present inventiondescribed above.

The present invention provides new and nonobvious armor which is neitherdisclosed in nor suggested by U.S. Pat. No. 7,041,372 (incorporatedfully herein for all purposes). This patent has no teaching orsuggestion to use carbon nanotubes, graphene or graphene ribbon-likematerial as taught by the present invention. Armor 370 according to thepresent invention as shown in FIG. 11 has an optional substrate 379 anda matrix 372 on the substrate 379 (when the substrate 379 is present).The matrix 372 includes unit components 376 which may be, e.g., anysuitable metal or ceramic, including, but not limited to, any suitablemetal or ceramic disclosed in U.S. Pat. No. 7,041,372; ceramic withribbons according to the present invention; or ceramic with ribbonsaccording to the present invention and carbon nanotubes. The matrix 372may be any suitable backing according to the present invention or anysuitable article according to the present invention as described above.

The substrate 379 may be any substrate as disclosed in U.S. Pat. No.7,041,372 or any suitable backing according to the present invention orany suitable article according to the present invention as describedabove.

As shown in FIG. 11 (not to scale), the matrix 372 has the units 376,optional carbon nanotubes 373, and ribbons 378.

The present invention provides new and nonobvious armored clothingneither disclosed in nor suggested by U.S. Pat. No. 5,996,115(incorporated fully herein for all purposes). This patent has noteaching or suggestion to use carbon nanotubes, graphene or ribbons astaught by the present invention. FIG. 12A shows a vest 400 according tothe present invention with a plurality of tiles 410, 412. The tiles 410,412 may be any tile according to the present invention described above.Parts of the vest 400—front 402, rear 404, sides 406, top 408, straps409—may be made of or contain, any suitable backing according to thepresent invention as described above. The sides 406 may include tiles403 (as any tile according to the present invention).

It is within the scope of the present invention to add nanotubes,crushed or not, and/or ribbon-like material to ballistic fabric.

The present invention, therefore, provides in some, but not innecessarily all embodiments, methods for making an armor article, themethods including: producing processed ceramic material by processingceramic material using a ceramic processing apparatus; producingprocessed nanotube material with a nanotube processing apparatus, thenanotube material being carbon nanotube material; introducing theprocessed ceramic material and the processed nanotube material into amold forming a processed mixture of processed ceramic material withprocessed nanotube material; compressing the processed mixture in themold with sufficient pressure to transform the processed nanotubematerial into transformed material, producing a compressed mixture;heating the compressed mixture to sinter together the processed ceramicmaterial with transformed material therein, producing asintered-together item; and the cooled sintered-together item being anarmor article. Such a method may have one or some, in any possiblecombination, of the elements, features, steps, characteristics oraspects as claimed in the claims submitted herewith.

The present invention, therefore, provides in some, but not innecessarily all embodiments, a method for making an armor article, themethod including: producing processed ceramic material by processingceramic material using a ceramic processing apparatus; producingprocessed nanotube material with a nanotube processing apparatus, thenanotube material comprising carbon nanotube material; introducing theprocessed ceramic material and the processed nanotube material into amold forming a processed mixture of processed ceramic material withprocessed nanotube material; compressing the processed mixture in themold with sufficient pressure to transform the processed nanotubematerial into transformed material, producing a compressed mixture;heating the compressed mixture to sinter together the processed ceramicmaterial with transformed material therein, producing asintered-together item; cooling the sintered-together item producing anarmor article; the ceramic material being alumina; the nanotube materialbeing multi-walled nanotubes; the mixture of ceramic material andnanotube material in the mold between 0.1% to 1.0% by weight nanotubematerial; and the transformed material being graphene ribbon-likematerial.

The present invention, therefore, provides in some, but not innecessarily all embodiments, armor having ceramic material, the ceramicmaterial having therein transformed nanotube material; and thetransformed nanotube material produced by subjecting a matrix of theceramic material and nanotube material to sufficient pressure andsufficient heat to transform the nanotube material. Such armor may haveone or some, in any possible combination, of the elements, features,steps, characteristics or aspects as claimed in the claims submittedherewith.

The present invention, therefore, provides in some, but not innecessarily all embodiments, armor having a plurality of adjacent tiles;each tile including ceramic material, the ceramic material havingtherein transformed nanotube material, and the transformed nanotubematerial produced by subjecting a matrix of the ceramic material andnanotube material to sufficient pressure and sufficient heat totransform the nanotube material.

The present invention, therefore, provides in some, but not innecessarily all embodiments, armor having a plurality of stacked tiles;each tile including ceramic material, the ceramic material havingtherein transformed nanotube material, and the transformed nanotubematerial produced by subjecting a matrix of the ceramic material andnanotube material to sufficient pressure and sufficient heat totransform the nanotube material.

The present invention, therefore, provides in some, but not innecessarily all embodiments, armor structure including: a first layer; asecond layer; and a third layer; at least one of the first layer, secondlayer and third layer being an armor including ceramic material, theceramic material having therein transformed nanotube material, and thetransformed nanotube material produced by subjecting a matrix of theceramic material and nanotube material to sufficient pressure andsufficient heat to transform the nanotube material. Such an armorstructure may have one or some, in any possible combination, of theelements, features, steps, characteristics or aspects as claimed in theclaims submitted herewith.

The present invention, therefore, provides in some, but not innecessarily all embodiments, an armor article having ceramic material,the ceramic material having therein transformed nanotube material, andthe transformed nanotube material produced by subjecting a matrix of theceramic material and nanotube material to sufficient pressure andsufficient heat to transform the nanotube material, wherein the armorarticle is one of rod, tile, insert, plate, blade, key, nut, bolt, hook,gear, chain link, screw, bearing, drill bit, bit seal, mill, reamer,pipe, universal joint, pliers, tool, backing, disc, panel, cylinder,pyramid, sphere, cone, knife, bearing structure, bit body, mill body,reamer body, cutting blade, milling blade, reaming blade, cutter,cutting insert, valve body, valve member, valve seat, ball, pipethreaded area, and bit roller cone.

In conclusion, therefore, it is seen that the present invention and theembodiments disclosed herein and those covered by the appended claimsare well adapted to carry out the objectives and obtain the ends setforth. Certain changes can be made in the subject matter withoutdeparting from the spirit and the scope of this invention. It isrealized that changes are possible within the scope of this inventionand it is further intended that each element or step recited in any ofthe following claims is to be understood as referring to the stepliterally and/or to all equivalent elements or steps. The followingclaims are intended to cover the invention as broadly as legallypossible in whatever form it may be utilized. The invention claimedherein is new and novel in accordance with 35 U.S.C. §102 and satisfiesthe conditions for patentability in §102. The invention claimed hereinis not obvious in accordance with 35 U.S.C. §103 and satisfies theconditions for patentability in §103. This specification and the claimsthat follow are in accordance with the requirements of 35 U.S.C. §112.The inventors may rely on the Doctrine of Equivalents to determine andassess the scope of their invention and of the claims that follow asthey may pertain to apparatus and/or methods not materially departingfrom, but outside of, the literal scope of the invention as set forth inthe following claims. All patents and applications identified herein areincorporated fully herein for all purposes. It is the express intentionof the applicant not to invoke 35 U.S.C. §112, paragraph 6 for anylimitations of any of the claims herein, except for those in which theclaim expressly uses the words ‘means for’ together with an associatedfunction. In this patent document, the word “comprising” is used in itsnon-limiting sense to mean that items following the word are included,but items not specifically mentioned are not excluded. A reference to anelement by the indefinite article “a” does not exclude the possibilitythat more than one of the element is present, unless the context clearlyrequires that there be one and only one of the elements.

What is claimed is:
 1. A method for making an armor article, the method comprising producing processed ceramic material by processing ceramic material using a ceramic processing apparatus, producing processed nanotube material with a nanotube processing apparatus, the nanotube material comprising carbon nanotube material, introducing the processed ceramic material and the processed nanotube material into a mold forming a processed mixture of processed ceramic material with processed nanotube material, compressing the processed mixture in the mold with sufficient pressure to transform the processed nanotube material into transformed material, producing a compressed mixture, heating the compressed mixture to sinter together the processed ceramic material with transformed material therein, producing a sintered-together item, and cooling the sintered-together item, said item comprising an armor article.
 2. The method of claim 1 wherein the processing apparatus produces ceramic material with a median size between 10 nanometers and 100 microns.
 3. The method of claim 1 wherein the processing ceramic material has a surface area between 3.5 to 4.5 square meters per gram.
 4. The method of claim 1 wherein the nanotube processing apparatus deagglomerates the nanotube material.
 5. The method of claim 1 wherein the ceramic material is alumina, the nanotube material is multi-walled nanotubes, and the mixture of ceramic material and nanotube material in the mold is between 0.1% to 1.0% by weight nanotube material.
 6. The method of claim 5 wherein the processed mixture is compressed at between 10,000 psi and 100,000 psi, and the compressed mixture is sintered at about 1600 degrees C. for 0.5 hours to 24 hours.
 7. The method of claim 1 wherein the transformed material is graphene ribbon-like material.
 8. The method of claim 1 further comprising the armor article comprising a binder sheet.
 9. The method of claim 8, the armor article comprising a layer of ballistic fabric adhered to the binder sheet.
 10. The method of claim 9 wherein the transformed material is graphene ribbon-like material and the binder sheet is a thermoplastic sheet of thermoplastic material with 10 milligrams of carbon nanotubes per each 3 grams of thermoplastic material.
 11. The method of claim 1 further comprising producing a plurality of armor articles according to the method of claim 1, each armor article comprising a binder sheet, interleaving a plurality of ballistic fabric layers with the binder sheets, and adhering the binder sheets to adjacent ballistic fabric layers.
 12. The method of claim 11 wherein the ballistic fabric layers are 0.0001 inches to 0.01 inches thick, and the binder sheets are between 0.0001 inches and 0.01 inches thick.
 13. The method of claim 11 wherein the armor article comprises a binder sheet, the binder sheet having two sides, the method further comprising applying a laminate layer to each side of the binder sheet, pressing the binder sheet and laminate layers together while heating, producing a pressed together combination, and cooling the pressed together combination forming a backing.
 14. The method of claim 13 wherein the binder sheet and the laminate layers are pressed together at between 100 psi and 10,000 psi, the heating is at between 25 degrees C. and 300 degrees C., and the backing is between 0.1 inch to 10 inches thick.
 15. The method of claim 13 further comprising adhering a plurality of tiles to the backing.
 16. The method of claim 15 wherein each tile comprises an armor article made by the method of claim
 1. 17. The method of claim 15 wherein the tiles are stacked in a pattern on the backing.
 18. The method of claim 1 wherein the armor article is fashioned as a plate.
 19. The method of claim 1 wherein the armor article is one of rod, tile, insert, plate, blade, key, nut, bolt, hook, gear, chain link, screw, bearing, drill bit, bit seal, mill, reamer, pipe, universal joint, pliers, tool, backing, disc, panel, cylinder, pyramid, sphere, cone, knife, bearing structure, bit body, mill body, reamer body, cutting blade, milling blade, reaming blade, cutter, cutting insert, valve body, valve member, valve seat, ball, pipe threaded area, and bit roller cone.
 20. A method for making an armor article, the method comprising producing processed ceramic material by processing ceramic material using a ceramic processing apparatus, producing processed nanotube material with a nanotube processing apparatus, the nanotube material comprising carbon nanotube material, introducing the processed ceramic material and the processed nanotube material into a mold forming a processed mixture of processed ceramic material with processed nanotube material, compressing the processed mixture in the mold with sufficient pressure to transform the processed nanotube material into transformed material, producing a compressed mixture, heating the compressed mixture to sinter together the processed ceramic material with transformed material therein, producing a sintered-together item, cooling the sintered-together item producing an armor article, the ceramic material is alumina, the nanotube material is multi-walled nanotubes, the mixture of ceramic material and nanotube material in the mold is between 0.1% to 1.0% by weight nanotube material, and the transformed material is graphene ribbon-like material. 